CN115172048B - Leadless barium titanate-based X9R type ceramic capacitor material and preparation method thereof - Google Patents
Leadless barium titanate-based X9R type ceramic capacitor material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 50
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 39
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 29
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims abstract description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 37
- 239000000919 ceramic Substances 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229920003023 plastic Polymers 0.000 claims description 14
- 239000004033 plastic Substances 0.000 claims description 14
- 244000137852 Petrea volubilis Species 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 238000000643 oven drying Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 238000004506 ultrasonic cleaning Methods 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 239000003989 dielectric material Substances 0.000 abstract description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 238000003746 solid phase reaction Methods 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 7
- 239000012071 phase Substances 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 101000872083 Danio rerio Delta-like protein C Proteins 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 230000000881 depressing effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Ceramic Engineering (AREA)
- Chemical & Material Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Capacitors (AREA)
Abstract
The invention discloses a leadless barium titanate-based X9R ceramic capacitor material and a preparation method thereof, wherein the chemical formula of the material is 0.85BaTiO 3 ‑0.15Bi(Mg 0.5 Hf 0.5 )O 3 ‑0.3wt％MnCO 3 The preparation method comprises collecting BaCO 3 、TiO 2 ﹑Bi 2 O 3 、HfO 2 BaTiO preparation by MgO 3 Bi (Mg) 0.5 Hf 0.5 )O 3 Finally, baTiO 3 、Bi(Mg 0.5 Hf 0.5 )O 3 And 3wt% MnCO 3 And (3) proportioning according to the standard stoichiometry of the chemical formula, ball milling, refining raw materials, presintering, secondary ball milling and the like, and finally preparing the temperature-stable X9R ceramic capacitor dielectric material by utilizing the solid phase reaction and carbonate decomposition process. The material can meet the requirement that X9R meets the requirement (delta C/C) within the temperature range of-55 ℃ to 200 DEG C 25 ) Less than or equal to +/-15 percent, and has the characteristics of wide working temperature and high stability.
Description
Technical Field
The invention relates to the technical field of dielectric ceramic application, in particular to a lead-free barium titanate-based X9R type ceramic capacitor material and a preparation method thereof.
Background
In recent decades, due to increasing demands for energy and increasing importance on environmental protection, development of novel lead-free high-performance dielectric capacitors that are environmentally friendly has become important. One of the key factors in achieving a clean, renewable energy system is the high performance energy storage device, while dielectric capacitors have become one of the most important components in electronic devices due to their ultra-high charge and discharge performance.
With the rapid development of modern electronics and microelectronics technologies, electronic component designs tend to be miniaturized, high-frequency, integrated, and applied in wide temperature fields, and ceramic capacitors are required to have wider temperature stability and lower loss. Current multilayer ceramic capacitors (MLCCs) are mainly of two types, X7R and X8R, with upper limit temperatures of 125 ℃ and 150 ℃ respectively, according to the Electronic Industry Association (EIA) class II dielectric standard, and fail when the service temperature exceeds its limit temperature due to failure to provide temperature stable dielectric properties. The rate of capacitance change DeltaC/C25.degreeC15% is not more than 15% in the temperature range from-55 to 200 ℃ for the X9R type MLCC, so that the research and development of the X9R type MLCC dielectric ceramic with higher temperature stability has been attracting great interest of scientists in recent years. However, most X9R-type MLCC ceramic dielectrics are lead-based relaxor ferroelectrics, which are not environmentally friendly and healthy. Based on the method, the lead-free X9R type MLCC ceramic medium is developed, so that the method not only has important application value, but also has great environmental protection significance.
The current high-capacity lead-free temperature stable MLCC mainly comprises barium titanate (BaTiO 3, BT for short), which is a classical ferroelectric material with perovskite structure at room temperature, and has higher dielectric constant and lower dielectric loss at room temperature. However, the dielectric constant near the Curie point varies greatly, and the requirement of delta C/C of 25 ℃ to +/-15% cannot be met within the temperature range of-55 ℃ to 200 ℃. It is necessary to broaden the curie peak to meet EIA-X9R characteristics while shifting the curie peak to a high temperature. The existing researches prove that few elements except elements such as lead, bismuth and the like can greatly raise the Curie temperature of the barium titanate, and most elements are doped to enable the Curie point of the barium titanate to move to low temperature. Therefore, there is no study for shifting the curie peak to a high temperature.
Disclosure of Invention
The invention aims to provide a lead-free barium titanate-based X9R type ceramic capacitor material and a preparation method thereof, which have excellent temperature stability, have the temperature change rate within the temperature range of-55 to +200 ℃ not exceeding the range requirement of +/-15 percent, and meet the temperature stability requirement of the X9R type ceramic capacitor dielectric material.
In one aspect of the invention, the invention provides a lead-free barium titanate-based X9R ceramic capacitor material. According to an embodiment of the present invention, the barium titanate BaTiO is made of tetragonal phase barium titanate 3 、Bi(Mg 0.5 Hf 0.5 )O 3 And 0.3wt% MnCO 3 The nominal chemical formula of the composition is 0.85BaTiO-0.15Bi (Mg 0.5 Hf 0.5 )O 3 -0.3wt％MnCO 3 。
In addition, the lead-free barium titanate-based X9R ceramic capacitor material according to the embodiment of the invention can also have the following additional technical characteristics:
in some embodiments of the invention, the lead-free barium titanate-based X9R ceramic capacitor material satisfies a temperature change rate DeltaC/C in a temperature range of-55 to 200 DEG C 25℃ The dielectric constant is between 906 and 1031 at room temperature, and the dielectric loss at room temperature is not more than 0.36 percent.
In another aspect of the invention, the invention provides a method for preparing a lead-free barium titanate-based X9R ceramic capacitor material. According to an embodiment of the invention, the method comprises the following steps:
(1) BaCO with analytical purity of more than 99 percent 3 And TiO 2 According to the following steps of 1:1, mixing the raw materials in a molar ratio, putting the mixed raw materials into a ball mill, adding a ball grinding medium, mixing, ball milling, and drying to obtain a dried powder 1;
(2) Heating the baked powder 1 prepared in the step (1) to 1000-1150 ℃ at a speed of 5 ℃/min for presintering for 4-6 hours to prepare pre-sintered BT powder;
(3) Bi with analytical purity of more than 99 percent 2 O 3 、HfO 2 Mixing MgO with ball milling medium as initial material, ball milling, stoving to obtain stoving powder 2;
(4) Presintering the dried powder 2 obtained in the step (3) to obtain presintered Bi (Mg) 0.5 Hf 0.5 )O 3 Powder;
(5) BT powder prepared in the steps (2) and (4) and Bi (Mg) 0.5 Hf 0.5 )O 3 Grinding the powder respectively, and grinding the rootAccording to chemical formula 0.85BaTiO 3 -0.15Bi(Mg 0.5 Hf 0.5 )O 3 -0.3wt％MnCO 3 Proportioning, ball milling with absolute ethyl alcohol as a ball milling medium, drying and grinding into powder after ball milling;
(6) Adding the binder into the powder prepared in the step (5) for granulating, tabletting and forming to obtain a ceramic plastic body, and discharging colloid to the ceramic plastic body;
(7) Calcining the ceramic-plastic blank body obtained in the step (6), and cooling to room temperature;
(8) Polishing the surface of the ceramic plastic blank body obtained in the step (7), ultrasonically cleaning the surface by alcohol, coating a layer of silver paste on the surface, drying and firing to obtain the lead-free barium titanate-based X9R ceramic capacitor material.
In addition, the preparation method of the lead-free barium titanate-based X9R ceramic capacitor material according to the embodiment of the invention can also have the following additional technical characteristics:
in some embodiments of the present invention, in the step (1), the mixed ball milling uses zirconia balls and absolute ethyl alcohol as media, and the mixed ball milling is performed for 10-24 hours; oven-drying at 80deg.C for 12 hr.
In some embodiments of the present invention, in the step (3), the method is performed according to Bi 2 O 3 ：HfO 2 : mgo=0.075: 0.075: mixing materials according to a molar ratio of 0.075, mixing and ball milling for 12-24 hours by taking absolute ethyl alcohol as a ball milling medium, and drying at 80 ℃ for 12 hours to prepare a dried powder 2;
in the step (4), the presintering process is specifically as follows, and the presintering process is carried out for 6 hours after the temperature is raised to 700-850 ℃ at the speed of 5 ℃/min.
In some embodiments of the present invention, in the step (3), the mixed ball mill uses zirconia balls and absolute ethyl alcohol as media to grind and uniformly mix the powder, and the mixed ball mill is performed for 10-24 hours.
In some embodiments of the present invention, in the step (5), the ball milling time is 12 hours, the drying temperature is 80 ℃, and the drying time is 12 hours.
In some embodiments of the present invention, in the step (6), 2-8wt% of polyvinyl alcohol aqueous solution is added as a binder, and the tabletting is performed in a die with a diameter of 14mm, and the ceramic plastic body is discharged after the temperature is kept at 400-600 ℃ for 1-2 hours.
In some embodiments of the invention, in the step (7), the calcination temperature is 1250-1350 ℃ and the calcination time is 2-4 hours.
In some embodiments of the invention, in the step (8), the surface of the ceramic-plastic body is polished with 1200 mesh sand paper; and then polishing the ceramic surface by using 2000-mesh sand paper, and ultrasonically cleaning by using alcohol, wherein the firing process is to fire at 600 ℃ for 30 min.
Compared with the prior art, the invention has the beneficial effects that:
1) The ceramic dielectric material provided by the invention has excellent temperature stability, the temperature change rate of the ceramic dielectric material within the temperature range of-55 ℃ to +200 ℃ does not exceed the range requirement of +/-15%, and the temperature stability requirement of the X9R type ceramic capacitor dielectric material is met.
2) The preparation method is simple, and the material preparation method adopts the traditional solid phase method, so that the reaction condition is easy to control and the repeatability is high; the equipment used is simple, the operation is easy, the cost is low, the large-scale production can be realized, and the method has good industrialization prospect.
3) Equivalent doping can achieve the effects of widening and depressing the Curie peak of barium titanate while moving the Curie temperature of barium titanate-based ceramics, mg in the invention 2+ With Mn 2+ The acceptor doped ions can weaken spontaneous polarization of the whole material and improve the temperature stability of the dielectric material. Therefore, B-site complex cation (Mg) 0.5 Hf 0.5 ) 3+ Bi with A-position 3+ Formation of Bi (Mg) 0.5 Hf 0.5 )O 3 With Mn 2+ And BT matrix solid solution to raise its curie temperature and broaden its curie peak.
4) The invention develops an X9R type ceramic capacitor dielectric material with low loss, high dielectric constant and high temperature stability based on lead-free barium titanate, which is beneficial to expanding the material type of MLCC.
5) The invention adopts a two-step synthesis method, and can partially avoid volatilization of Bi element in the presintering process.
Drawings
FIG. 1 is a diagram showing 0.85BaTiO prepared in example 1 of the present invention 3 -0.15Bi(Mg 0.5 Hf 0.5 )O 3 -0.3wt％MnCO 3 An X-ray spectrum of the material;
FIG. 2 shows 0.85BaTiO according to example 1 of the present invention 3 -0.15Bi(Mg 0.5 Hf 0.5 )O 3 -0.3wt％MnCO 3 Photomicromorphology of the material;
FIG. 3 is a diagram showing 0.85BaTiO according to example 1 of the present invention 3 -0.15Bi(Mg 0.5 Hf 0.5 )O 3 -0.3wt％MnCO 3 A plot of dielectric constant of the material as a function of temperature;
FIG. 4 shows 0.85BaTiO according to example 1 of the present invention 3 -0.15Bi(Mg 0.5 Hf 0.5 )O 3 -0.3wt％MnCO 3 Temperature profile of a material.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention uses BaTiO 3 And Bi (Mg) 0.5 Hf 0.5 )O 3 0.3wt% MnCO 3 The raw materials are sintered together to form a ceramic. BaTiO 3 The powder is used as basic raw material, and B-site composite cation (Mg 0.5 Hf 0.5 ) 3+ Bi with A-position 3+ Ion formation of Bi (Mg) 0.5 Hf 0.5 )O 3 With Mn 2+ And BT matrix solid solution to form solid solution.
Example 1
The preparation method of the leadless barium titanate-based X9R type ceramic capacitor material comprises the following steps:
(1) BaCO is carried out 3 (99%) and TiO 2 (99%) according to 1:1 moleMixing the materials according to the molar ratio, putting the materials into a ball milling tank, selecting zirconia balls and a nylon tank, mixing and milling for 12 hours at the rotating speed of 300r/min, and preparing dry powder 1 by using absolute ethyl alcohol as a ball milling medium;
(2) The obtained product is placed in an oven at 80 ℃ for drying for 12 hours, and is heated to 1100 ℃ at a heating rate of 5 ℃/min for presintering for 6 hours, so as to obtain pre-sintered BT powder;
(3) Bi is mixed with 2 O 3 (99％)、HfO 2 (99.9%) and MgO (99%) were as per Bi 2 O 3 ：HfO 2 : mgo=0.075: 0.075: mixing materials according to a molar ratio of 0.075, putting the materials into a ball milling tank, selecting zirconia balls and a nylon tank, mixing and milling for 12 hours at a rotating speed of 300r/min, and preparing a dried powder 2 by using absolute ethyl alcohol as a ball milling medium;
(4) The obtained product is dried in an oven at 80 ℃ for 12 hours, and is presintered for 6 hours after rising to 750 ℃ at a heating rate of 5 ℃/min, thus obtaining the presintered Bi (Mg) 0.5 Hf 0.5 )O 3 Powder;
(5) Taking out the two pre-burned powders, grinding, and grinding according to chemical formula 0.85BaTiO 3 -0.15Bi(Mg 0.5 Hf 0.5 )O 3 -0.3wt％MnCO 3 Mixing materials, ball milling with absolute ethyl alcohol as ball milling medium for 12h, mixing uniformly, drying at 80 ℃ for 12h, and grinding into powder;
(6) Pressing the uniformly mixed powder into a circular ceramic blank body with the diameter of 14mm and the thickness of 1mm by a single-shaft tablet press;
(7) Granulating with 5% polyvinyl alcohol aqueous solution as binder, pressing into a circular sheet-shaped plastic body with diameter of 14mm and thickness of 1mm under 60MPa, heating to 600deg.C at a heating rate of 1deg.C/min, and maintaining for 2 hr to discharge colloid;
(8) Placing the ceramic blank in a high-temperature resistance furnace, heating to 1300 ℃ from room temperature at a heating rate of 5 ℃/min, sintering for 2 hours, and cooling to room temperature along with the furnace;
(9) And polishing the surface of the ceramic by using 1200-mesh sand paper, ultrasonically cleaning the ceramic by using alcohol, finally coating a layer of silver paste on the surface of the ceramic, drying, and then preserving heat for 30min at 600 ℃ to fire, thereby preparing the lead-free barium titanate-based X9R temperature stable ceramic capacitor dielectric material.
Bi (Mg) is selected in the invention 0.5 Hf 0.5 )O 3 The doping element is mainly based on the following mechanism: mg in doping element 2+ With Mn 2+ The acceptor doped ions can weaken spontaneous polarization of the whole material, improve the temperature stability of the dielectric material and improve the Curie temperature of the dielectric material. While Hf 4+ The ion can equivalently replace Ti 4+ The ion and equivalent doping can achieve the effects of widening and depressing the Curie peak of barium titanate while moving the Curie temperature of the barium titanate-based ceramics. A narrow and single (200) peak can also be seen from the X-ray pattern of fig. 1, demonstrating that B-site ion doping plays a major role, and that the main crystalline phase of the material has been transformed from tetragonal phase to pseudocubic phase.
From the photomicrograph of FIG. 2, a clear grain boundary structure and a dense surface can be observed. This can be attributed to the doping of 0.3wt% MnCO during sintering 3 Liquid phase is formed on the grain boundary, so that the material transmission is promoted, the density of the dielectric ceramic body is improved, and the loss is reduced. Compared with pure phase barium titanate, the crystal grain size of the invention is greatly reduced.
Fig. 3 and 4 are temperature dependency graphs of dielectric constants and temperature characteristic diagrams of the present invention, respectively. It can be seen that the dielectric material meets the EIAX9R standard requirement and has good dielectric properties, wherein the dielectric constant at room temperature is about 1025 and the dielectric loss at room temperature (25 ℃) is only 0.36%. This is due to Bi 3+ Ions are few doping elements which can move the Curie peak to the high temperature end, and the high Curie temperature ensures that the invention has stronger high temperature end stability.
Example 2
The preparation method of the leadless barium titanate-based X9R type ceramic capacitor material comprises the following steps:
(1) BaCO is carried out 3 (99%) and TiO 2 (99%) according to 1:1 molar ratio, putting the mixture into a ball milling tank, selecting zirconia balls and a nylon tank, mixing and ball milling for 24 hours at the rotating speed of 300r/min, and preparing dry powder 1 by using absolute ethyl alcohol as a ball milling medium;
(2) The obtained product is placed in an oven at 80 ℃ for drying for 12 hours, and is heated to 1100 ℃ at a heating rate of 5 ℃/min for presintering for 2 hours, so as to obtain pre-sintered BT powder;
(3) Bi is mixed with 2 O 3 (99％)、HfO 2 (99.9%) and MgO (99%) were as per Bi 2 O 3 ：HfO 2 : mgo=0.075: 0.075: mixing materials according to a molar ratio of 0.075, putting the materials into a ball milling tank, selecting zirconia balls and a nylon tank, mixing and milling for 24 hours at a rotating speed of 300r/min, and preparing a dried powder 2 by using absolute ethyl alcohol as a ball milling medium;
(4) The obtained product is dried in an oven at 80 ℃ for 12 hours, and is presintered for 4 hours after rising to 750 ℃ at a heating rate of 5 ℃/min, thus obtaining the presintered Bi (Mg) 0.5 Hf 0.5 )O 3 Powder;
(5) Taking out the two pre-burned powders, grinding, and grinding according to chemical formula 0.85BaTiO 3 -0.15Bi(Mg 0.5 Hf 0.5 )O 3 -0.3wt％MnCO 3 Mixing materials, ball milling with absolute ethyl alcohol as ball milling medium for 12h, mixing uniformly, drying at 80 ℃ for 12h, and grinding into powder;
(6) Pressing the uniformly mixed powder into a circular ceramic blank body with the diameter of 14mm and the thickness of 1mm by a single-shaft tablet press;
(7) Granulating with 5% polyvinyl alcohol aqueous solution as binder, pressing into a circular sheet-shaped plastic body with diameter of 14mm and thickness of 1mm under 60MPa, heating to 600deg.C at a heating rate of 1deg.C/min, and maintaining for 2 hr to discharge colloid;
(8) Placing the ceramic blank in a high-temperature resistance furnace, heating to 1270 ℃ from room temperature at a heating rate of 5 ℃/min, sintering for 2 hours, and cooling to room temperature along with the furnace;
(9) And polishing the surface of the ceramic by using 1200-mesh sand paper, polishing the surface of the ceramic by using 2000-mesh sand paper, ultrasonically cleaning the surface of the ceramic by using alcohol, finally coating a layer of silver paste on the surface of the ceramic, drying, and then preserving heat for 30min at 600 ℃ for firing, thereby preparing the lead-free barium titanate-based X9R temperature stable ceramic capacitor dielectric material.
The foregoing is merely illustrative and explanatory of the invention, as it is well within the scope of the invention, as it is intended to provide those skilled in the art with various modifications, additions and substitutions to the specific embodiments disclosed and those skilled in the art without departing from the scope of the invention as disclosed in the accompanying claims.
Claims (10)
1. The preparation method of the lead-free barium titanate-based X9R type ceramic capacitor material is characterized by comprising the following steps of:
(1) BaCO with analytical purity of more than 99 percent 3 And TiO 2 According to the following steps of 1:1, mixing the raw materials in a molar ratio, putting the mixed raw materials into a ball mill, adding a ball grinding medium, mixing, ball milling, and drying to obtain a dried powder 1;
(2) Heating the baked powder 1 prepared in the step (1) to 1000-1150 ℃ at a speed of 5 ℃/min for presintering for 4-6 hours to prepare pre-sintered BT powder;
(3) Bi with analytical purity of more than 99 percent 2 O 3 、HfO 2 Mixing MgO with ball milling medium as initial material, ball milling, stoving to obtain stoving powder 2;
(4) Presintering the dried powder 2 obtained in the step (3) to obtain presintered Bi (Mg) 0.5 Hf 0.5 )O 3 Powder;
(5) BT powder prepared in the steps (2) and (4) and Bi (Mg) 0.5 Hf 0.5 )O 3 Grinding the powder respectively, and grinding according to chemical formula 0.85BaTiO 3 -0.15Bi(Mg 0.5 Hf 0.5 )O 3 -0.3wt％MnCO 3 Compounding, wherein the weight percentage of MnCO is 0.3wt% 3 0.85BaTiO3-0.15Bi (Mg) 0.5 Hf 0.5 )O 3 -0.3wt％MnCO 3 0.3% of the mass, ball milling by taking absolute ethyl alcohol as a ball milling medium, and drying and grinding into powder after ball milling;
(6) Adding the binder into the powder prepared in the step (5) for granulating, tabletting and forming to obtain a ceramic plastic body, and discharging colloid to the ceramic plastic body;
(7) Calcining the ceramic-plastic blank body obtained in the step (6), and cooling to room temperature;
(8) Feeding the surface of the ceramic plastic blank body obtained in the step (7)Polishing, ultrasonic cleaning with alcohol, coating a layer of silver paste on the surface, oven drying, and firing to obtain leadless barium titanate-based X9R ceramic capacitor material with nominal chemical formula of 0.85BaTiO-0.15Bi (Mg) 0.5 Hf 0.5 )O 3 -0.3wt％MnCO 3 。
2. The method for preparing the lead-free barium titanate-based X9R ceramic capacitor material according to claim 1, wherein the method comprises the following steps: in the step (1), zirconium oxide balls and absolute ethyl alcohol are used as media for mixing ball milling, and the mixing ball milling is carried out for 10-24 hours; oven-drying at 80deg.C for 12 hr.
3. The method for preparing the lead-free barium titanate-based X9R ceramic capacitor material according to claim 1, wherein the method comprises the following steps: in the step (3), according to Bi 2 O 3 ：HfO 2 : mgo=0.075: 0.075: mixing and ball milling for 12 hours by taking zirconia balls and absolute ethyl alcohol as ball milling media after the mixture is proportioned according to the molar ratio of 0.075, and drying for 12 hours at 80 ℃ to prepare a dried powder 2;
in the step (4), the presintering process is specifically as follows, and the presintering process is carried out for 4-6 hours after the temperature is raised to 700-850 ℃ at the speed of 5 ℃/min.
4. The method for preparing the lead-free barium titanate-based X9R ceramic capacitor material according to claim 1, wherein the method comprises the following steps: in the step (3), zirconia balls and absolute ethyl alcohol are used as media for grinding and uniformly mixing powder for mixed ball milling for 10-24 hours.
5. The method for preparing the lead-free barium titanate-based X9R ceramic capacitor material according to claim 1, wherein the method comprises the following steps: in the step (5), the ball milling time is 12 hours, the drying temperature is 80 ℃, and the drying time is 12 hours.
6. The method for preparing the lead-free barium titanate-based X9R ceramic capacitor material according to claim 1, wherein the method comprises the following steps: in the step (6), 2-8wt% of polyvinyl alcohol aqueous solution is added as a binder, tabletting is carried out in a die with the diameter of 14mm, and the ceramic plastic body is discharged after the temperature is kept at 400-600 ℃ for 1-2 h.
7. The method for preparing the lead-free barium titanate-based X9R ceramic capacitor material according to claim 1, wherein the method comprises the following steps: in the step (7), the calcination temperature is 1250-1350 ℃ and the calcination time is 2h.
8. The method for preparing the lead-free barium titanate-based X9R ceramic capacitor material according to claim 1, wherein the method comprises the following steps: in the step (8), the surface of the ceramic-plastic blank body is polished by using 1200-mesh sand paper; and then polishing the ceramic surface by using 2000-mesh sand paper, and ultrasonically cleaning by using alcohol, wherein the firing process is to fire at 600 ℃ for 30 min.
9. A lead-free barium titanate-based X9R-type ceramic capacitor material prepared by the method of preparing a lead-free barium titanate-based X9R-type ceramic capacitor material according to any one of claims 1 to 8.
10. A lead-free barium titanate-based X9R ceramic capacitor material in accordance with claim 9, wherein: the leadless barium titanate-based X9R ceramic capacitor material meets the condition that the capacitance temperature change rate is delta C/C within the temperature range of-55-200 DEG C 25℃ The dielectric constant is between 906 and 1031 at room temperature, and the dielectric loss at room temperature is not more than 0.36 percent.
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